United States Patent (19) 11 Patent Number: 5,034,441 Nakano Et Al

United States Patent (19) 11 Patent Number: 5,034,441 Nakano et al. 45 Date of Patent: Jul. 23, 1991

54 STYRENE-BASED RESIN COMPOSITION (56. References Cited AND PROCESS FOR PRODUCING U.S. PATENT DOCUMENTS MOLDING PRODUCTS THEREOF 4,463,113 7/1984 Nakahara et al...... 524/117 4,619,959 10/1986 Matsubara et al...... 524/228 75) Inventors: Akikazu Nakano; Takashi Sumitomo, 4,680,353 7/1987 Ishihara et al...... 526/59 both of Ichihara, Japan 4,820,772 4/1989 Goto et al...... 524/117 73 Assignee: Idemitsu Kosan Co., Ltd., Tokyo, Primary Examiner-Joseph L. Schofer Japan Assistant Examiner-Mark D. Sweet Attorney, Agent, or Firm-Frishauf, Holtz, Goodman & (21) Appl. No.: 559,971 Woodward 57 ABSTRACT (22 Filed: Jul. 27, 1990 Disclosed is a styrene-based resin composition which comprises (a) 100 parts by weight of styrene-based poly Related U.S. Application Data mer having a high degree of syndiotactic configuration, 63 Continuation-in-part of Ser. No. 470,975, Jan. 26, 1990, (b) 0.01 to 15 parts by weight of at least one nucleating abandoned. agent selected from an organophosphorus compound and a metal salt of an organic acid, and (c) 0.01 to 15 (30) Foreign Application Priority Data parts by weight of at least one component selected from a polyoxyalkylene compound, a fatty acid and a deriva Feb. 2, 1989 (JP) Japan ...... 1-22587 tive thereof. 51 Int. Cli...... C08K 5/15 The composition can produce various molding prod 52 U.S. C...... 524/117; 524/127; ucts with excellent mold-releasing property, surface 524/377; 524/385; 524/388; 524/307; 524/228; gloss, bending strength, bending modulus and heat resis 524/577; 524/394 tance. 58) Field of Search ...... 524/117, 127, 228,377, 524/385, 388 6 Claims, No Drawings 5,034,441 1. 2 Another object of the present invention is to provide STYRENE-BASED RESIN COMPOSITION AND a process for efficiently producing the molding product PROCESS FOR PRODUCING MOLDING with excellent properties described above. PRODUCTS THEREOF The present invention provides a styrene-based resin 5 composition which comprises (a) 100 parts by weight of This application is a continuation-in-part of U.S. ap styrene based polymer having a high degree of syndi plication Ser. No. 07/470,975, filed Jan. 26, 1990, now otactic configuration, (b) 0.01-15 parts by weight of a abandoned. nucleating agent consisting of at least one component selected from an organophosphorus compound and a BACKGROUND OF THE INVENTION 10 metal salt of an organic acid, and (c) 0.01-15 parts by 1. Field of the Invention weight of at least one component selected from a poly The present invention relates to a styrene-based resin oxyalkylene compound, a fatty acid and a derivative composition and process for producing molding prod thereof. The present invention also provides a process ucts thereof, more specifically it relates to a styrene for producing molded products (molding products) based resin composition which comprises a styrene 15 which process comprises molding said styrene-based based polymer having a high degree of syndiotactic resin composition with a die at a low temperature. configuration and specific components mixed there The styrene-based resin composition in the present with, and a process for producing molding products invention is composed essentially of (a), (b) and (c). prepared from the composition, which has a high crys Here, the syndiotactic configuration in styrene-based tallinity, an excellent surface gloss property and an 20 polymer of the (a) component means that its stereo excellent mold-releasing property. chemical structure is a syndiotactic configuration, i.e., 2. Description of the Related Arts having a stereo structure in which phenyl groups or A styrene based polymer produced by the radical substituted phenyl groups are located as side chains polymerization method, etc. has an atactic configura alternatively in opposite directions relative to the main tion in stereostructure. It is molded into various shapes 25 by various molding methods such as injection molding, chain consisting of carbon-carbon bonds. Tacticity is extrusion molding, blow molding, vacuum forming and quantitatively determined by the nuclear magnetic reso flow-in molding, for example, and is widely used for nance method using a carbon isotope (13C-NMR electric domestic appliances, office equipments, domes method). tic appliances, packaging, toys, furnitures, synthetic 30 The tacticity, as determined by the 13C-NMR papers and other industrial materials. However, the method, can be indicated in terms of the proportions of styrene-based polymer having an atactic configuration structural units connected continuously to each other, has drawbacks of insufficient mechanical strength, heat i.e., a diad in which two structural units are connected resistance and chemical resistance since it is not crystal to each other, a triad in which three structural units are lized. 35 connected to each other, or a pentad in which five The group of the present inventors have succeeded to structural units are connected to each other. The sty develop a styrene-based polymer having a high degree rene-based polymers having a high degree of syndiotac of syndiotacticity, and also developed a composition in tic configuration have such a syndiotactic configuration which other components are blended with the styrene that the proportion of racemic diad is at least 75% and based polymer (Japanese Patent Application Laid-Open preferably at least 85%, or the proportion of racemic Nos. 1048.18/1987,257948/1987 and 257950/1987). This pentad is at least 30% and preferably at least 50% in styrene-based polymer having a high degree of syndi syndiotacticity. The styrene-based polymers having a otactic configuration or a composition thereof has ex high degree of syndiotactic configuration in the present cellent mechanical strength, heat resistance, solvent invention include polystyrene, poly(alkylstyrene), resistance and electric characteristic as compared with 45 poly(halogenated styrene), poly(alkoxystyrene), poly(- a styrene-based polymer having an atactic configuration vinyl benzoate ester) and mixtures thereof, and copoly and its composition. However, the molding product mers containing them as main components. The above obtained by using the styrene-based polymer having a poly(alkyl styrene) includes poly(methylstyrene), poly high degree of syndiotacticity as a raw material requires (ethylstyrene), poly(isopropylstyrene), poly(tert-butyls high molding temperature to crystallize. 50 tyrene), poly(vinyl benzene), etc, and the poly(- In Japanese Patent Application Laid-Open No. halogenated styrene) includes poly(chlorostyrene), 201350/1989, there is proposed to accelerate the crys poly(bromostyrene), poly(fluorostyrene), etc. The tallization of a styrene-based polymer having a syndi poly(alkoxystyrene) also includes poly(methoxysty otactic configuration by blending a specific nucleating rene), poly(ethoxystyrene), etc. The most preferred agent, and the mold-releasing property and appearance 55 styrene-based polymers are polystyrene, poly(p-meth of the molding products therefrom have been im ylstyrene), poly(m-methylstyrene), poly(tert-butyl sty proved. rene), poly(p-chlorostyrene), poly(m-chlorostyrene), According to this technique, while physical proper poly(p-fluorostyrene), and a copolymer of styrene and ties or appearance of the composition or the molding p-methylstyrene. products obtained can be improved, there remains some 60 The molecular weight of the styrene-based polymer problems that crystallization rate is insufficiently high used in the present invention is not critical, but the and surface gloss of the molding products is poor. weight average molecular weight is preferably at least 10,000, and most preferably at least 50,000. The molecu SUMMARY OF THE INVENTION lar weight distribution is not critical, and the styrene An object of the present invention is to provide a 65 based polymers in various ranges of molecular weight styrene-based resin composition which can produce a can be applied. Styrene-based polymer with a weight molding product having a high crystallinity and a good average molecular weight of less than 10,000 is not appearance. suitable because the composition obtained and its 5,034,441 3 4. molded products have inferior thermal characteristics an alkyl group having 1 to 6 carbon atoms, and M and and mechanical strength. a are the same as defined above). The styrene-based polymers having a syndiotactic Specific examples of the organophosphorus com configuration can be produced by polymerizing sty pounds (b) represented by the general formula above rene-based monomers (corresponding to the above sty 5 (B-I) are shown below: rene-based polymers) using a catalyst comprising a tita nium compound and a condensate of water and trialkyl aluminium in, for example, an inert hydrocarbon sol O vent or in the absence of a solvent (Japanese Patent O- P-O-Na. Application Laid Open No. 187708/1987). 10 The component (b) of the resin composition in the 2 present invention consists of any one or both of a metal salt of an organic acid and an organophosphorus com O pound. The metal salt of an organic acid includes so I dium, calcium, aluminium or magnesium salt of benzoic 15 O- P-O-Ca/2 acid, p-(tert-butyl) benzoic acid, cyclohexane carbox 2 ylic acid (hexahydrobenzoic acid), amino benzoic acid, A-naphthoic acid, cyclopentane carboxylic acid, suc cinic acid, diphenyl acetic acid, glutaric acid, isonico tinic acid, adipic acid, sebacic acid, phthalic acid, iso 20 phthalic acid, benzene sulfonic acid, glycolic acid, ca (al-O-o- |-- proic acid, isocaproic acid, phenyl acetic acid, cinnamic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. In particular, aluminium salt of 25 p-(tert-butyl) benzoic acid, sodium salt of cyclohexane carboxylic acid and sodium salt of g-naphthoic acid, etc., are preferred. The preferred organophosphorus compounds are O organophosphorus compounds (b1) represented by the 30 general formula: (-O-o- P-O-Cal/ O (B-I) O 35 P-O-Ca/ (-O-o- 2 (wherein R represents a hydrogen or an alkyl group having 1 to 18 carbon atoms, R2 represents an alkyl group having 1 to 18 carbon atoms,

45 or M1/a, M represents Na, K, Mg, Ca or Al, and a repre sents an atomic valence of M) and organophosphorus O O compounds (b2) represented by the general formula: 50 I/ N t-An o-P Ca N / R3 (B-II) O

O O 55 I R4 \ CH3 --o-Msia R y- Aa O CH O --O-can O-C3H17 R4 R3 65 (wherein R represents a methylene group, an ethylidene CH3 o-i-o-ca group, a propylidene group or an isopropylidene group, Rand Rindependently represent a hydrogen atom or 5,034,441 5 6 -continued -continued t-Bu

t-Bu O- P-O-Al1/3 5 C2H5 O 2 \ CH2 P-O-Na. In connection with the organophosphorus com pounds (b2) represented by the general formula (B-II), 0 there are a variety of compounds depending on the type C2H5 O of R, R3, and R and M represented by the formula above. R3 and R independently represent a hydrogen 15 t-Bu atom or an alkyl group having 1 to 6 carbon atoms. t-Bu Examples of the alkyl group are a methyl group, an ethyl group, an isopropyl group, a n-butyl group, an CH3 O isobutyl group, a sec-butyl group, a tert-butyl group, a 20 \ n-amyl group, a tert-amyl group, and a hexyl group. CH2 P-O-Na Specific examples of organophosphorus compounds / (b2) are shown below: 25 CH3 O

t-Bu t-Bu

t-Bu t-Bu O 30 \ t-Bu O CH2 P-O-Na O / 35 CH2 P-O-Ca1/2 t-Bu O / t-Bu O t-Bu 40 t-Bu t-Bu t-Bu

t-Bu O \ 45 s-Bu O O CH3-CH /P-O-Na CH3-CH2 P-O-Na

t-Bu- O 50 s-Bu O

t-Bu t-Bu t-Bu 55 CH3

i-Pr O CH3 O \ 60

i-Pr O CH3 O 65

t-Bu CH3 5,034,441 8 -continued thereof are markedly reduced in heat resistance and t-Bu chemical-resistance, and thus are unsuitable for practi cal use. The resin composition of the present invention com t-Bu O prises, in addition to the above components (a) and (b), a polyoxyalkylene compound and/or a fatty acid or a O derivative thereof as the component (c). Polyoxyalkyl ene compound includes a polyoxyethylene compound, CH3-CH y a polyoxypropylene compound and various compounds 10 having a recurring unit of polyoxyalkylene group with t-Bu O 2 to 5 carbon atoms. Among these compounds, a com pound represented by the general formula: t-Bu t-Bu 15 (wherein R7 and R8 are each a hydrogen or an alkyl group having 1 to 4 carbon atoms, n is an integer of 4 to t-Bu O 450, preferably 15 to 45), and alkyl ethers thereof such as polyoxyethylene monomethyl ether, polyoxyethyl O ene dimethyl ether, polyoxyethylene diethyl ether and polyoxyethylene dipropyl ether are preferred. Among CH3-CH y those alkyl ethers, polyoxyethylene dimethyl ether is most preferred. The molecular weight of the polyoxy t-Bu O ethylene compound described above is 200 or more, 25 preferably 500 to 20,000, and most preferably 700 to 2,000. t-Bu As for the component (c), a fatty acid or a derivative -Bu thereof can be used singly or in combination with the 30 polyoxyalkylene compound. As the fatty acid, a fatty acid having 1 to 31 carbon atoms can be used, and more t-Bu O specifically, it includes a saturated fatty acid such as formic acid, acetic acid, propionic acid, n-butyric acid, \ n-valeric acid, caproic acid, enanthic acid, caprylic 35 acid, pelargonic acid, capric acid, undecylic acid, lauric CH-CH y acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadeca t-Bu O noic acid, arachic acid, behenic acid, lignoceric acid, serotic acid, heptacosanic acid, montanic acid, melissic t-Bu acid, lacceroic acid, and an unsaturated fatty acid such as acrylic acid, crotonic acid, isocrotonic acid, undecy t-Bu lenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassidic acid, sorbic acid, linolic acid, linolenic acid, arachidonic acid, propyolic acid, stearolic acid. t-Bu O 45 Among these, a fatty acid having 10 to 24 carbon atoms is preferred. \ As fatty acid derivatives, oxy fatty acid, fatty acid amide, alkylenebis fatty acid amide and fatty acid ester CH2 y can be used. These derivatives have 1 to 31 carbon 50 atoms, preferably 10 to 24 carbon atoms in the fatty acid portion. The oxy fatty acid is an acid wherein hydrogen -C- O at a hydrocarbon portion of the fatty acid mentioned t-Bu above is substituted by a hydroxyl group, the fatty acid amide is that wherein the carboxyl group of the above In the present invention, the component (b) compris 55 fatty acid is modified to amide (for example, behenic ing a metal salt of an organic acid and an organophos acid amide), and the fatty acid ester is that wherein the phorus compound works as a nucleating agent in order above fatty acid is esterified with an alcohol. to accelerate the crystallinity of the component (a), the In the present invention, among these fatty acid de styrene-based polymers having a high degree of syndi rivatives, alkylene-bis-fatty acid amide is most prefera otactic configuration. The amount of the nucleating bly used. The alkylene-bis-fatty acid amide is repre agent added is 0.01 to 15 parts by weight, preferably sented by the following general formula: 0.05 to 10 parts by weight per 100 parts by weight of the component (a). If the amount of the component (b) R-CONH-(CH2)n-NHOC-R6 added is less than 0.01 part by weight, the effect for accelerating the crystallinity of the styrene-based poly 65 wherein R* and Reach represent identical or different mers described above can hardly be expected. On the hydrocarbon portion of the fatty acid, m is an integer of other hand, if it is in excess of 15 parts by weight, the 1 to 10. A preferred example of the alkylene-bis-fatty resulting resin composition or the molded products acid amide includes methylene-bis-stearic acid amide, 5,034,441 9 10 ethylene-bis-stearic acid amide and ethylene-bis phenone series, external lubricants such as fatty carbox behenic acid amide. ylic acid ester series and paraffinic series, convention In the resin composition of the present invention, the ally used nucleating agents, mold-releasing agents, anti component (c) works to accelerate crystallinity of the static agents, colorants etc. Synthetic resins mentioned resin composition and improve mold-releasing prop 5 above include polyethylene, polypropylene, polysty erty. The amount of the component (c) added is 0.01 to rene, AS-resin, ABS-resin, polymethylmethacrylate, 15 parts by weight, preferably 0.05 to 10 parts per 100 polyphenylene ether, polyphenylene sulfide, polyam parts by weight of the component (a). If the amount of ide, polyarylate, polycarbonate etc. Addition of various the component (c) added is less than 0.01 part by elastomers thereto is also effective. weight, the effect of accelerating the crystallinity of the O In the preparation of the resin composition of the above resin composition can hardly be expected. As the present invention, the above components (a) to (c) and result, improvements of crystallinity, mold-releasing other desired components are compounded and mixed property and appearance of the molded products can at a room temperature or are blended by various meth not be accomplished. On the other hand, if it is in excess ods such as melt-kneading. More specifically, the melt of 15 parts by weight, the mechanical strength, elastic 15 kneading method using a kneader, a mixing roll, an ity and heat resistance of the resulting resin composition extruder, a Banbury mixer, a Henschel mixer and or molded products thereof are markedly reduced. kneading roll, or the solution blending method etc., can When the mixing ratio (weight ratio) of the compo be employed. nent (b): the component (c) in the present composition is In the resin composition of the present invention, it is selected in the range of 1:1 to 1:100, preferably 1:2 to 20 preferred that recrystallization peak measured by a 1:50, a markedly higher effect for accelerating crystal differential scanning calorimeter (DSC) either disap linity can be achieved. peared, or the temperature of recrystallization peak The resin composition of the present invention is (Tc) is 170° C. or lower, specifically 150 to 90° C., and composed essentially of the components (a), (b) and (c) peak area (crystallizing enthalpy on heating) (AHTCC) is as the main components, and if necessary, and inorganic 25 2 cal/g or less. filler can be optionally added. In the process for producing molding products in the The inorganic filler may be any of fibrous, granular present invention, the styrene-based resin composition or power in form. Examples of the fibrous filler include described above can be molded at a low temperature, glass fiber, carbon fiber, and alumina fiber. Of these specifically at room temperature to 200' C., more pref fibers, glass fiber and carbon fiber are particularly pre 30 erably at a die temperature of 60' to 160° C. The tem ferred. The shape of the glass fiber can be either cloth perature of a resin composition when molding is not like, mat-like, strand-like, short fiber-like or filament specifically restricted, but preferably it is heated and like. Of these fibers, strand-like glass fiber having a molten at a temperature of the melting point to 360° C. length of 0.05 to 13 mm and a fiber diameter of 5 to 15 A suitable molding method can be selected according um is preferred. Most preferred is a strand-like glass 35 to the molding products to be produced, and various fiber subjected to silane treatment. A polyacrylonitrile thermal molding methods for the conventional styrene (PAN)-based fiber is preferred as a carbon fiber. Bun based polymer having an atactic configuration, for ex dles of chopped PAN fiber with a length of about 3 mm ample press molding, injection molding, blow molding, . and a diameter of 7 to 15 um are more preferred. vacuum molding, flow-in molding, cast molding, flow As examples of granular or powder inorganic fillers, spreading molding, coating molding, spinning molding, there may be mentioned talc, carbon black, graphite, impregnation molding, coating molding such as dip titanium dioxide, silica, mica, calcium carbonate, cal ping, brushing and spraying methods, and uniaxial or cium sulfate, barium carbonate, magnesium carbonate, biaxial (sequential or simultaneous) stretching etc. can magnesium sulfate, barium sulfate, oxysulfate, tin oxide, be used alumina, kaolin, silicon carbide and metal powder. Of 45 As mentioned above, according to the present inven these fillers, talc, calcium carbonate, and mica are most tion, the styrene-based composition in which crystalli preferred. The average particle diameter of talc is pref. zation of the syndiotactic polystyrene is accelerated can erably 0.3 to 20 um, more preferably 0.6 to 10 um. The be obtained. Further, by molding said composition with average particle diameter of calcium carbonate is pref a die (mold) at a relatively low temperature, molding erably 0.1 to 20 um. The average particle diameter of 50 products having high mold-releasing property, crystal mica is preferably 40 to 250 lm, and more preferably 50 linity and surface gloss, as well as excellent in bending to 150 um. strength, bending modulus and heat resistance, can be The inorganic filler described above is added in a prepared. ratio of 1 to 550 parts by weight, preferably 4 to 200 Accordingly, the resin composition and the molding parts by weight per 100 parts by weight of the above the products obtained of the present invention can be component (a). If the amount of the inorganic filler widely and effectively utilized for such various fields as added is less than 1 part by weight, a sufficient effect as general construction materials, electric and electronic filler cannot be expected. On the other hand, if it is in parts, and automotive parts, as well as film, fiber, sheets excess of 500 parts by weight, the inorganic filler cannot etc. be dispersed uniformly, whereby the resulting composi The present invention is described in greater detail tion might be inferior in mechanical strength. with examples and reference examples as follows. To the resin composition of the present invention can be added various additives or various synthetic resins, REFERENCE EXAMPLE 1 as well as the above components (a)-(c) and the inor (Preparation of Polystyrene having a Syndiotactic ganic filler, if it does not impair the purpose of this 65 Configuration) invention. The above additives include antioxidants Two liters (L) of toluene as a solvent, and 5 mmol of such as phosphite ester series and phosphate ester series, tetraethoxytitanium and 500 mmol (as aluminum atom) UV ray adsorbers such as benzotriazole series or benzo of methylaluminoxane as catalyst components were 5,034,441 11 12 placed in a reactor, and 15 L of styrene were introduced thereinto and polymerized for 4 hours at 55 C. Gloss of Surface After completion of the polymerization, the reaction It was measured according to JIS-K-7105. product was washed with a mixture of hydrochloric Mold-releasing properties acid and methanol to decompose and remove the cata 5 lyst components, and was then dried to obtain 2.5 kg of It was evaluated by the following standard. a styrene polymer (syndiotactic polystyrene). The poly O... easily released from the mold mer was subjected to Soxhlet extraction using methyl A... deformed when releasing from the mold ethyl ketone as a solvent to obtain 97% by weight of an X . . . unable to be released from the mold extraction residue. The weight average molecular 10 weight of the polymer was 400,000 and the number Crystallinity average molecular weight was 180,000. Melting point of It was measured by DSC. the polymer was 269 C. A 13C-NMR analysis (solvent: 1,2-dichlorobenzene) showed an absorption at 145.35 Bending strength and bending modulus ppm, ascribable to the syndiotactic configuration, and 15 They were measured according to JIS-L-7203. the syndiotacticity indicated in terms of racemic pentad as calculated from the peak area was 98%. Vicat softening point EXAMPLE It was measured according to JIS-K-7206. EXAMPLES 2 to 19 One hundred parts by weight of polystyrene having a 20 syndiotactic configuration obtained in Reference Exam The test pieces were prepared and evaluated in the ple 1, 0.7 parts by weight of (2,6-di-tert-butyl-4-methyl same manner as in Example 1 except that components phenyl) pentaerythritol diphosphite (Trade Mark: PEP shown in Table 1 were compounded in prescribed 36, produced by Adeca Argus Co., Ltd.) and 0.1 parts amounts. The results are shown in Table 2. by weight of 2,6-di-tert-butyl-4-methylphenol (Trade 25 Mark: SUMILIZER BHT, produced by Sumitomo COMPARATIVE EXAMPLES 1 to 6 Chemical Industry Co., Ltd.) as antioxidants, 1 part by The test pieces were prepared and evaluated in the weight of aluminum p-(tert-butyl) benzoate (Trade same manner as in Example 1 except that components Mark: PTBBA-Al, produced by Dainippon Ink & shown in Table 1 were compounded in prescribed Chemicals Inc.) and 4 parts by weight of polyoxyethyl 30 amounts. The results are shown in Table 2. ene dimethyl ether (weight average molecular weight Marks in Table 1 mean the following: 1,000, produced by Nippon Oil & Fats Co., Ltd.) were *1 Aluminum p-(tert-butyl) benzoate: PTBBA-Al, mixed, dry-blended and pelletized using a twin-screw produced by Dainippon Ink & Chemicals Inc. extruder. The mixing ratio of the components described "2 Bis(4-tert-butylphenyl) sodium phosphate: NA above are shown in Table . 35 10, produced by Adeca Argus Co., Ltd. Injection molding was carried out using pellets ob *3 Methylene-bis (2,4-di-tert butyl phenyl) sodium tained at a die temperature of 100° C., then dumbbell phosphate: NA-11, produced by Adeca Argus Co., Ltd. test pieces were prepared for a bending test and flat "4 Sodium stearate plates were prepared for evaluating mold-releasing *5 Polyoxyethylene dimethyl ether: a trial produc property. Furthermore, recrystallization peak, gloss of 40 tion, produced by Nippon Oil & Fats Co., Ltd, weight surface, crystallinity, bending strength, bending modu average molecular weight 1,000. lus and Vicat softening point were tested. The results *6 Polyoxyethylene monomethyl ether: UNIOX M are shown in Table 2. 550, produced by Nippon Oil & Fats Co., Ltd, weight Each of the characteristics is measured by the follow average molecular weight 550. ing procedure. 45 *7 Polyoxyethylene: PEG 4000, produced by Nippon Oil & Fats Co., Ltd, weight average molecular weight Recrystallization peak 4,000 A sample of 10 mg obtained by cutting a pellet was *8 Ethylene-bis-behenic acid amide: NPO-2, pro placed in a pan for measuring DSC, heated at the rate of duced by Nippon Oil & Fats Co., Ltd. 20 C./min under a nitrogen atmosphere, maintained at 50 *9 Ethylene-bis-stearic acid amide: EB-P, produced 300 C. for 5 minutes and melted. by KAO Co., Ltd. After that, the sample in the pan was quenched at the *10 Behenic acid amide: produced by Nippon Oil & rate of 100 C./sec in a dry ice-methanol bath. Fats Co., Ltd. Then, the sample in the pan was heated to 300° C. at *11 Metablen IP-2, produced by Mitsubishi Rayon the rate of 20 C./min under the nitrogen atmosphere. 55 Co., Ltd. styrene grafted butadiene rubber, particle size The exothermic peak generated at that time means the 0.7 um. recrystallization peak (Tcc), and the peak area AHTCC *12 Chopped strand CS 03 MA 429A, produced by was measured by integration. Asahi Fiber Glass Co., Ltd, an average fiber length 3 mm, average fiber diameter 13 um. 60 *13 Talc; FFR, produced by Asada Seifun Co., Ltd, average particle diameter: 0.6 um. TABLE 1. Organophosphorus Styrene-based compound or salt Polyoxyethylene Fatty acid Inorganic polymer of organic acid compound derivative Elastomer filler NO. (parts by weight) (parts by weight) (parts by weight) (parts by weight) (parts by weight) (parts by weight) Example OO 11 4'5 5,034,441 13 14 TABLE 1-continued Organophosphorus Styrene-based compound or salt Polyoxyethylene Fatty acid Inorganic polymer of organic acid compound derivative Elastomer filler NO. (parts by weight) (parts by weight) (parts by weight) (parts by weight) (parts by weight) (parts by weight) Example 2 100 11 m 4'8 m - Example 3 100 11 45 18 o m Example 4 00 0.21 4's - Example 5 00 0.21 0.45 0.48 o Example 6 100 11 9'5 m o Example 7 100 11 o 98 Example 8 100 11 45 48 m --- Example 9 100 *2 4'5 18 --- - Example 10 100 13 4's 18 o --- Example 11 100 14 4's 1's M Example 12 100 11 4'6 18 m Example 13 00 11 47 1's wo Example 14 00 1*1 O 49 Example 15 100 11 45 110 m Example 16 100 12 4's 19 2011 o Example 17 100 13 4's *10 o 43' 12 Example 18 100 13 4'5 1"10 2011 10'13 Example 19 100 11 4'5 1's M-- 160'12 40'13 Comparative 100 M wr- ma o Example 1 Comparative 100 10'i o o m Example 2 Comparative 00 11 20'5 20'8 o Example 3 Comparative 100 - eu- m 2011 Example 4 Comparative 100 re 43' 12 Example 5 Comparative 100 -- m- 2011 1013 Example 6

TABLE 2 Recrystallization peak Glass of Mold-releasing Crystal- Bending strength Bending modulus Vicat softening No. (°C) (cal/g) surface property linity (%) (kg/cm) (kg/cm) point (C.') Example 1 100 1.7 100 O 48 1,010 41,000 245 Example 2 124 1.4 00 O 49 1,020 41,300 246 Example 3 Disappeared 0 100 O 53 1,050 42,000 256 Example 4 28 .9 00 O 48 1,010 40,900 246 Example 5 112 0.7 00 O 51 1,040 41,800 254 Example 6 120 1.2 00 O 50 1,030 40,000 252 Example 7 12 1.3 00 O 50 1,030 40,100 25 Example 8 Disappeared O 100 O 55 1,050 42,200 257 Example 9 Disappeared 0. 100 O 52 1,030 41,700 25 Example 10 Disappeared 0 100 O 53 1,020 4,600 254 Example ll Disappeared 0 100 O 53 1,030 41,700 253 Example 12 109 0.5 100 O 5 1,010 40,900 250 Example 13 106 0.4 100 O 51 1,000 40,800 250 Example 14 121 1.2 100 O 48 1,010 40,600 249 Example 15 Disappeared O 100 O 52 1,040 42,100 253 Example 16 - 0 100 O 52 970 38,000 246 Example 17 - 0 87 O 53 1,570 104,000 260 Example 18 -- 0 93 O 52 1,240 56,000 246 Example 19 - 0 81 O 53 1,650 157,000 266 Comparative 159 5.0 60 X 12 890 37,400 224 Example 1 Comparative 145 2.5 75 A 28 950 40,500 234 Example 2 Comparative - 0. 100 O 55 870 36,000 238 Example 3 Comparative 158 4.9 62 X 13 860 35,800 218 Example 4 Comparative 158 5.0 60 X 15 1,480 95,800 256 Example 5 Comparative 157 4.9 62 A 4. 530 45,000 211 Example 6 What is claimed is: organic acid, and (c) 0.01 to 15 parts by weight of at 1. A styrene-resin composition which comprises (a) least one component selected from a polyoxyalkylene 100 parts by weight of styrene-polymer having a high 65 compound, a fatty acid and a derivative thereof, and degree of syndiotactic configuration, (b) 0.01 to 15 parts wherein a recrystallization peak of said composition by weight of at least one nucleating agent selected from measured by a differential scanning calorimeter an organophosphorus compound and a metal salt of an (DSC) disappears, or the temperature of the recrys 5,034,441 15 16 tallization peak (Tcc) is 170° C. or lower, and peak wherein R represents a methylene group, an ethylidene area (AHtcc) is 2 cal/g or less. group, a propylidene group or an isopropylidene group, 2. A styrene resin composition according to claim 1, R3 and Rindependently represent a hydrogen atom or wherein the organophosphorus compound is a com an alkyl group having 1 to 6 carbon atoms, and M and pound represented by the general formula (B-I): 5 a are the same as defined above. 3. A styrene resin composition according to claim 1, wherein the metal salt of the organic acid is sodium, (B-I) calcium, aluminium or magnesium salt of benzoic acid, p-(tert-butyl) benzoic acid, cyclohexane carboxylic acid R1 o-i-o-M, O (hexahydrobenzoic acid), amino benzoic acid, 6-naph O-R2 thoic acid, cyclopentane carboxylic acid, succinic acid, diphenyl acetic acid, glutaric acid, isonicotinic acid, (wherein R represents a hydrogen or an alkyl group adipic acid, sebacic acid, phthalic acid, isophthalic acid, having 1 to 18 carbon atoms, R2 represents an alkyl benzene sulfonic acid, glycolic acid, caproic acid, isoca group having 1 to 18 carbon atoms, 15 proic acid, phenyl acetic acid, cinnamic acid, lauric acid, myristic acid, palmitic acid, stearic acid, or oleic acid. 4. A styrene resin composition according to claim 1, wherein the fatty acid derivative of the component (C) 20 is an oxy fatty acid, a fatty acid amide, an alkylene-bis fatty acid amide or a fatty acid ester. or M1/a, M represents Na, K, Mg, Ca or Al, and a repre 5. A styrene-based resin composition according to sents an atomic valence of M) or represented by the claim 1, wherein the polyoxyalkylene compound is a general formula (B-II): polyoxyethylene compound represented the general 25 formula: R3 (B-II)

O wherein R7 and R8 are each a hydrogen or an alkyl 30 group having 1 to 4 carbon atoms, n is an integer of 4 to 450. 6. A styrene-based resin composition according to R P-O-M/ claim 1, wherein the fatty acid derivative is an alkylene bis-fatty acid amide represented by the general formula: / 35 O R4 wherein Rand R6 are each hydrocarbon portion of the fatty acid, and m is an integer of 1 to 10. k k k +